Process for the boiling-off and bucking of cellulose fibers in aqueous alkaline solution containing r-(oc2h4)nu och2 coom compounds



United States P t O i 5...... A...

1 2,802,715 PROCESS FOR THE BOILING-OFF AND BUCKING F CELLULOSE FIBERSIN AQUEOUS ALKA- LINE SOLUTION CONTAINING R-(OC2H4)B OCH: COOM COMPOUNDSKurt Hofer, Neue Welt, near Basel, and Hans Hemmi, Binningen, nearBasel, Switzerland, assignors, by mesne assignments, to Saul & Co.,Newark, N. J., as nominee of Fidelity Union Trust Company No Drawing.Application May 3, 1954, Serial No. 427,366 Claims priority, applicationSwitzerland May 6, 1953 Claims. (Cl. 8-139) The present invention isconcerned with the cleaning of cellulose fibers as for example those inthe so-called gray state, more especially by boiling-off and bucking.

A primary object of the invention is the embodiment of a cleaningprocess of the character aforesaid, whereby the boiling-off and/orbucking may proceed in more eflicient manner and whereby the treatedfibers are better suited for subsequent treatments, such asmercerization, bleaching, dyeing, finishing and the like.

This object is realized according to the present invention, brieflystate, by subjecting the cellulose fibers to treatment at temperaturesabove 75 C. in an alkaline bath containing polyether carboxylic compoundcorresponding to the formula wherein R stands for a saturated orunsaturated aliphatic hydrocarbon radical with 8 to carbon atoms or foran alkylaryl or hydrogenated alkylaryl radical with 8 to carbon atoms, nis a whole number which is greater than 1, and M represents a cation.Cellulose fibers thus created become highly wettable and do not losethis property upon being rinsed ro washed, boiled, mercerized orbleached. Accordingly, upon the further treatment of such fibers inaqueous media wherein good wetting and penetration normally requires theaddition of a wetting agent, it is possible according to the presentinvention successfully to carry out such further treatment withouthaving to add a wetting agent.

The thus-realizable rapid wettability makes it possible to carry outmercerizing, bleaching, dyeing, finishing and the like processes morequickly and more uniformly. Moreover, the presence of a compound ofFormula I facilitates the penetration of the boiling-oif and buckingliquors into the fibers, so that the boiling-oil or bucking processproceeds more rapidly and more uniformly.

This property of the aforesaid polyether carboxylic acid compounds (I)is surprising, since it cannot be realized at all or only to a greatlydiminished extent with the known bucking assistants such as thealkylaryl sulfonates,

the alkyl sulfates, the fatty acid condensation products,

etc.

Illustrative of compounds of Formula I which are particularly useful incarrying out the present invention are the following compounds:

1" zig meant that 11 may range from as low as to as high ascmrOowmomomcmo 00H, etc.

GsHWQ-(HCHgC momornooon Oumowmornomcrnooon Example I A cotton cretonnefabric, directly as it comes from the loom, is boiled-oil for two hoursin an aqueous caustic soda liquor of 2 B. strength in a goods to liquorratio of 1:40 in an open vessel in the presence in the liquor of onegram of sodium oleyl-dodecaglycoloxyacetate [CraHssO CHsCHaO 12CHzCOONa]per liter of liquor, after which the material is washed with hot Waterand then with cold water until it is neutral, whereupon it is dried at60 C. The material then has an excellent wettability in aqueous medium,which is not the case if the boiling-oil is carried out in the absenceof the said compound.

Example 2 Unboiled cotton is boiled-off for two hours in an aqueouscaustic soda liquor of 2 B. strength in a goods to liquor ratio of 1:40in the presence in the liquor of one gram of sodiumoleyl-dodecaglycoloxyacetate per liter of liquor, after which thematerial is washed with hot water and then with cold water until it isneutral, whereupon it is dried. After this treatment, the material hasan excellent absorptive action.

Example 3 Gray cotton pearl yarn 3/2 is boiled-oil in an aqueous causticsoda liquor of 2 B. strength in a goods to liquor ratio of 1:40 for oneand one-half hours in an open vessel in the presence in the liquor ofone gram per liter of sodium oleyl-dodecaglycoloxyacetate, after whichthe material is Washed neutral and dried. By way of comparison, asimilar yarn is boiled-oil in an aqueous caustic soda liquor of 2 B.strength in the same bath ratio for 4 hours with no addition to theliquor. If these yarns are now subjected to comparative shrinking testsin caustic soda of 30 B. strength at 20 C., then the yarn which wasboiled-01f without the addition of assistant shows after seconds ashrinking of 12.2%, while that which was boiled-off with the assistantshows a shrinkage of 22%.

Example 4 Gray cotton pearl yarn 3/2 is boilechoff for one and one-halfhours in an aqueous caustic soda liquor of 2 B. strength, containing onegram of sodium lauryltetraglycoloxyacetate [C1zH35O(CH2CH2O)4CHzCOONu]per liter of liquor, in an open vessel. If this yarn is subjected to acomparative test, after the manner set forth in Example 3, with a likeyarn which was boiled-off under the same conditions but in the absenceof the added assistant, it will be found that the yarn treated with theassistant shrinks to an extent of 21.4% in 90 seconds while thatboiled-oft without the assistant shrinks only to an extent of 14.6%.

Example Cotton pearl yarn 3/2 in the gray is boiled-off for 2 hours inan aqueous caustic soda liquor of 2 B. strength, containing one gram ofsodium iso-octylphenylor is& octylhexahydrophenyloctaglycoloxyacetateper liter of liquor, in an open vessel. The material is thereupon rinsedand dried. Shrinkage measurements according to Example 3 show that, incontrast to the yarn which was boiled-ofi without the added assistantand which shrinks only about 12.8% under the given conditions, the yarnwhich was boiled-off with the assistant shrinks to an extent of 21.3% inthe same time (90 seconds).

Example 6 A piece of unboiled cotton cretonne is bucked for two hours inan aqueous caustic soda liquor of 2 B. strength under a pressure of oneand one-half atmospheres in the presence in the liquor of 0.25 gram ofsodium olcyldecaglycoloxyacetate with a goods to liquor ratio of 1:10.The material is then washed and dried. The thustreated piece of fabricwets very easily, while a similar piece of fabric which was bucked asabove but without the assistant shows only a very slight wettability.

Example 7 A piece of cotton cretonne, as it comes from the loom, isboiled-off for two hours in an aqueous caustic soda liquor of 2 B.strength in a goods to bath ratio of 1:40 in an open vessel with theaddition to the liquor of one gram per liter of sodiumlauryl-hexaglycoloxyacetate, after which the material is rinsed until ithas a neutral reaction and is then dried. This treatment impartsoutstanding wettability to the material. X

Example 8 A piece of cotton cretonne fabric is bucked for two hours at apressure of 1.8 atmospheres in a pressure receptable in an aqueouscaustic soda liquor of 2 B. strength containing one gram of sodiummyristyl-decaor cetyl-dodecaor stearyl-dodeca-glycoloxyacetate perliter. The material is then washed and dired. Even after repeatedwashings, the material still has outstanding wcttability.

Example 9 A piece of unboiled cotton cretonne is boiled-off for twohours in an aqueous caustic soda liquor of 2 B. strength in a goods tobath ratio of 1:40 and in an open vessel, with the addition to theliquor of 0.5 gram of sodium oleyldodecaglycoloxyacetate per liter ofliquor, after which the material is rinsed and dried. In contrast to apiece of this fabric which was boiled-off in the absence of theassistant, the treated piece can, in the padding process, by virtue ofrapid and very uniform wettability, he excellently padded on the Foulardwith a conventionally prepared vat-acid solution of dyestufi No. 1270(Schultz, Farbstofftabellen, 7th edition, 1931), the dyestuffpenetrating the material to be dyed in outstanding manner and theresulting dyeing being very even.

Example 10 1 Similar results may he obtained with sodiumtetramethylnonyloctaglyeoloxyacetate prepared from tetramethylnonanol(Enjay Co. Inc.. New York).

tion of dyestufi No. 513 (Schultz, Farbstofi'tabellen, 7th edition,1931), very uniform wetting is obtained and, upon completion of thedyeing, the material is very well through-dyed.

Example 11 Linen yarn is boiled-01f first for two hours in an aqueoussolution of 5 grams of calcined sodium carbonate and 0.2 gram of sodiumoleyl-dodecaglycoloxyacetate per liter, and then subjected to the actionof chlorine for one hour in the cold in a solution containing 5 grams ofactive chlorine per liter, acidified, aftertreated with sodiumbisulfite, and dried. In this way, an outstandingly absorptive anddyeable yarn is obtained, whereas linen yarn treated in the same mannerin the absence of the assistant has only a very slight absorptivecapacity.

Example 12 A difiicultly and non-uniformly wettable and swelling viscosefabric is boiled-off for one and one-half hours in a goods to bath ratioof 1:30 in a bath containing 1.0 gram of sodiumoleyl-dodecaglycoloxyacetate and 0.5 gram of a 30% aqueous caustic sodasolution per liter, after which the material is rinsed and dried. Thesor treated fabric is wetted and swells much more uniformly than thesame fabric which has been boiled-0E without assistant.

Example 13 A piece of cotton cretonne fabric, as it comes from the loom,is boiled-off for two hours in a goods to bath ratio of 1:40 in anaqueous caustic soda liquor to 2 B. strength in an open vessel, with theaddition to the bath of one gram of sodium oleyl-dodecaglycoloxyacetateper liter of liquor, after which the material is rinsed until it isneutral and then bleached in the cold for two hours with a bleachingliquor which contains one gram of active chlorine per liter, thenacidified, dechlorinated with sodium bisulfite, and dried. Thethus-treated fabric is, in comparison with like material which has beentreated without an assistant, much whiter.

Example 14 goods to bath ratio of 1:20 in an open vessel, with additionof one gram of sodium oleyl-dodecaglycoloxyacetate per liter of liquor,after which the yarn is washed neutral and dried. This yarn is thentreated for one hour, in the mercerized or unmercerized state, in achlorine bleaching bath containing one gram of active chlorine perliter, whereupon it is acidified, dechlorinated and then treated in anoxygenic bleaching bath which contains 10 milliliters of hydrogenperoxide (30%) and 1 milliliter of aqueous caustic soda solution (36 B.)per liter. The temperature is raised, in this connection, from 40 to 75C. in the course of two hours and, after a temperature of 75 C. isreached, maintained at one hour between 75 and C. The material is thenrinsed and dried. In this way, a very nice bleached yarn is obtained,whereas a pearl yarn which is similarly treated but without theassistant according to this invention has, after being bleached, aconsiderably inferior white appearance.

It will be evident from the foregoing examples that the treatmentaccording to the present invention is generally carried out at theboiling temperature of the aqueous alkaline treating bath, i. e. at atemperature above 75 C. However, for the sake of completeness, it may benoted that the treatment may be carried out at temperature within therange from 75 to C.

While, as is evident from the foregoing illustrative examples, it ispreferred to use the assistant (1) in the form of the sodium salt, suchassistant may also with essentially equal success be used in the form ofthe acid or of other soluble salts, for instance potassium, ammonium andamine salts of the acid.

The preferred aqueous alkaline treating bath is preferably constitutedby a caustic soda liquor of 2 B. strength, but the invention may withequal success be carried out with other alkaline boiling-off or buckingbaths, such as baths which density may vary from 0.5 to B. and whichinstead of caustic soda contain caustic potassium or sodium carbonate orpotassium carbonate.

The preferred concentration of assistant in the treating bath is 0.2 to1 gram per liter, but in some cases it may be favorable to reduce or toincrease the quantity of the assistant within the range of 0.1 to 10grams per liter.

Having thus disclosed the invention, what is claimed is:

l. A bucking process for cleaing gray cellulose fibers, which compriseswashing the gray cellulose fibers at temperatures of 75 to 140 C. withan aqueous alkaline solution of 0.5 to 10 B. containing as the essentialalkaline ingredient a member selected from the group consisting ofcaustic soda, caustic potash, sodium carbonate and potassium carbonate,and as another essential ingredient a compound of the formula R(OC2H4)nOCHzCOOM wherein R is a member selected from the group consisting ofsaturated and unsaturated aliphatic hydrocarbon radicals containing 8 tocarbon atoms, and alkylphenyl and hydrogenated alkylphenyl radicalscontaining a total of 8 to carbon atoms, n is a whole number which is 2to 20, and M represents a cation selected from the group consisting ofhydrogen, an alkali metal and ammonium, until impurities have beenremoved from the fibers and the latter have been rendered hydrophilic.

2. A bucking process for cleaning gray cellulose fibers, which compriseswashing the gray cellulose fibers at temperatures of 75 to 140 C. withan aqueous alkaline solution of 0.5 to 10 B. containing as the essentialalkaline ingredient a member selected from the group consisting ofcaustic soda, caustic potash, sodium carbonate and potassium carbonate,and as another essential ingredient a compound of the formula R (CC-2H4nOCH2COOM wherein R is a saturated aliphatic hydrocarbon radicalcontaining 8 to 20 carbon atoms, n is a whole number which is 2 to 20,and M represents a cation selected from the group consisting ofhydrogen, an alkali metal and ammonium, until impurities have beenremoved from the fibers and the latter have been rendered hydrophilic.

3. A bucking process for cleaning gray cellulose fibers, which compriseswashing the gray cellulose fibers at temperatures of 75 to 140 C. withan aqueous alkaline solution of 0.5 to 10 B. containing as the essentialalkaline ingredient a member selected from the group consisting ofcaustic soda, caustic potash, sodium carbonate and potassium carbonate,and as another essential ingredient a compound of the formula wherein Ris an unsaturated aliphatic hydrocarbon radical containing 8 to 20carbon atoms, n is a whole number which is 2 to 20, and M represents acation selected from the group consisting of hydrogen, an alkali metaland ammonium, until impurities have been removed from the fibers and thelatter have been rendered hydrophilic.

4. A bucking process for cleaning gray cellulose fibers, which compriseswashing the gray celluose fibers at temperatures of 75 to 140 C. with anaqueous alkaline solution of 0.5 to 10 B. containing as the essentialalkaline ingredient a member selected from the group consisting ofcausic soda, caustic potash, sodium carbonate and potassium carbonate,and as another essential ingredient a compound of the formula wherein Ris an alkylphenyl radical containing a total of 8 to 25 carbon atoms, nis a whole number which is 2 to 20, and M represents a cation selectedfrom the group consisting of hydrogen, an alkali metal and ammonium,until impurities have been removed from the fibers and the latter havebeen rendered hydrophilic.

5. A bucking process for cleaning gray cellulose fibers, which compriseswashing the gray cellulose fibers at temperatures of to C. with anaqueous alkaline solution of 0.5 to 10 B. containing as the essentialalkaline ingredient a member selected from the group consisting ofcaustic soda, caustic potash, sodium carbonate and potassium carbonate,and as another essential ingredient a compound of the formula wherein Ris a hydrogenated alkylphenyl radical containing a total of 8 to 25carbon atoms, 1': is a whole number which is 2 to 20, and M represents acation selected from the group consisting of hydrogen, an alkali metaland ammonium, until impurities have been removed from the fibers and thelatter have been rendered hydrophilic.

6. A buckling process for cleaning gray cellulose fibers, whichcomprises washing the gray cellulose fibers at temperatures of 75 to 140C. with an aqueous alkaline solution of 0.5 to 10 Be. containing as theessential alkaline ingredient caustic soda and as another essentialingredient sodium lauryl-hexaglycoloxyacetate, until impurities havebeen removed from the fibers and the latter have been renderedhydrophilic.

7. A buckling process for cleaning gray cellulose fibers, whichcomprises washing the gray cellulose fibers at temperatures of 75 to 140C. with an aqueous alkaline solution of 0.5 to 10 B. containing as theessential alkaline ingredient caustic soda and as another essentialingredient sodium myristyl-decaglycoloxyacetate, until impurities havebeen removed from the fibers and the latter have been renderedhydrophilic.

8. A bucking process for cleaning gray cellulose fibers, which compriseswashing the gray cellulose fibers at temperatures of 75 to 140 C. withan aqueous alkaline solution of 0.5 to 10 B. containing as the essentialalkaline ingredient caustic soda and as another essential ingredientsodium cetyl-dodecaglycoloxyacetate, until impurities have been removedfrom the fibers and the latter have been rendered hydrophilic.

9. A bucking process for cleaning gray cellulose fibers, which compriseswashing the gray cellulose fibers at temperatures of 75 to 140 C. withan aqueous alkaline solution of 0.5 to 10 B. containing as the essentialalkaline ingredient caustic soda and as another essential ingredientsodium stearyl-clodecaglycoloxyacetate, until impurities have beenremoved from the fibers and the latter have been rendered hydrophilic.

10. A bucking process for cleaning gray cellulose fibers, whichcomprises washing the gray cellulose fibers at temperatures of 75 to 140C. with an aqueous alkaline solution of 0.5 to 10 B. containing as theessential alkaline ingredient caustic soda and as another essentialingredient sodium oleyl-dodecaglycoloxyacetate, until impurities havebeen removed from the fibers and the latter have been renderedhydrophilic.

References Cited in the file of this patent UNITED STATES PATENTSHausmann et al. Dec. 19, 1939 Nusslein et a1. Feb. 8, 1944 OTHERREFERENCES

1. A BUCKING PROCESS FOR CLEANING GRAY CELLULOSE FIBERS, WHICH COMPRISESWASHING THE GRAY CELLULOSE FIBERS AT TEMPERATURES OF 75 TO 140*C. WITHAN AQUEOUS ALKALINE SOLUTION OF 0.5 TO 10*BE. CONTAINING AS THEESSENTIAL ALKALINE INGREDIENT A MEMBER SELECTED FROM THE GROUPCONSISTING OF CAUSTIC SODA, CAUSTIC POTASH, SODIUM CARBONATE ANDPOTASSIUM CARBONATE, AND AS ANOTHER ESSENTIAL INGREDIENTT A COMPOUND OFTHE FORMULA